Catalytic reforming catalyst activation

ABSTRACT

Catalyst activation of a platinum reforming catalyst system contained in a multiple reactor system by simultaneously reducing the catalyst with hydrogen while introducing a nonmetallic chlorine-containing compound into a reactor of the multiple reactor system in an amount to provide from about 0.05 to about 0.3 weight percent chlorine on the catalyst and thereafter purging the system with about 100 to about 50,000 cubic feet of hydrogen per cubic foot of catalyst resulting in a reforming system having increased activity and providing enhanced RON values with reduced cracking of feedstock.

[0001] This invention relates to the regeneration and activation ofreforming catalyst and the use of such activated catalyst in thereforming of hydrocarbons.

BACKGROUND OF THE INVENTION

[0002] Catalytic reforming, or hydroforming, is a well establishedindustrial process employed by the petroleum industry for improving theoctane quality of naphthas or straight run gasolines. In reforming, amulti-functional catalyst is employed which typically contains a metalhydrogenation-dehydrogenation (hydrogen transfer) component orcomponents, substantially atomically dispersed upon the surface of aporous inorganic oxide support, notably alumina.

[0003] In recent years, platinum has been widely commercially used asthe metallic hydrogen transfer component of reforming catalysts, andplatinum-on-alumina catalysts have been commercially employed inrefineries. Also, additional metallic components, such as rhenium,iridium, ruthenium, tin, palladium, germanium and the like, have beenadded to platinum as promoters to further improve the activity,selectivity, or both, of the basic platinum catalyst.

[0004] In a conventional reforming process, a series of reactorsconstitute the heart of the reforming unit. Each reforming reactor isgenerally provided with a fixed bed or beds of the catalyst whichreceive upflow or downflow feed. Each reactor is provided with a heaterbecause the reactions which take place therein are endothermic. In aconventional reforming process, a naphtha feed with hydrogen or hydrogenrecycle gas is passed through a preheat furnace, then downward through areactor, and then in sequence through subsequent interstage heaters andreactors of the series. The product of the last reactor is separatedinto a liquid fraction and a vaporous effluent. The vaporous effluent, agas rich in hydrogen, is used as hydrogen recycle gas in the reformingprocess.

[0005] During operation, the activity of the reforming catalystgradually declines due to the build-up of coke, and the temperature ofthe process is gradually raised to compensate for the activity losscaused by the coke deposits. Eventually, economics dictate the necessityof regenerating the catalyst.

[0006] The initial phase of catalyst regeneration is accomplished byburning the coke off the catalyst under controlled conditions. Catalystregeneration is then completed through a sequence of activation stepswherein the agglomerated metal hydrogenation-dehydrogenation componentsare atomically redispersed. Such activation generally is achieved bytreating the catalyst with hydrogen to effect reduction of the platinumoxide, and such other oxides as may be present in the catalyst system,followed by a chloride treatment of the reduced catalyst system prior toplacing it back into use.

[0007] In addition to the activation process required when working witha catalyst which has been subjected to regeneration by burning off cokefrom the catalyst, there is generally carried out an activationtreatment of the initially charged catalyst to the reactor prior to theintroduction of hydrocarbon feed to the system.

[0008] In both the activation of fresh catalyst as well as theactivation of a regenerated catalyst there have been numerous efforts toachieve a catalyst system whereby the catalyst will have increasedactivity, provide a product having increased octane values and avoid theundesirable cracking of product.

[0009] It is an object of the present invention to provide a process forthe regeneration and activation of a platinum reforming catalyst.

[0010] Another object of the invention is to provide an improved systemfor the activation of a platinum reforming catalyst whereby the catalystactivity is increased.

[0011] A still further object of this invention is to provide animproved process for the activation of a platinum reforming catalystwhich, when the activated catalyst is used in the reforming of areformer feed, the cracking of such feed to undesired byproducts isreduced.

[0012] Yet another object of this invention is to provide a process forthe activation of a platinum reforming catalyst which, when theactivated catalyst is used in the reforming of a reformer feed, thecracking of such feed is decreased while the octane number of thereformer product is increased.

[0013] Other aspects, objects and the several advantages of theinvention will be apparent from the following specification and appendedclaims.

SUMMARY OF THE INVENTION

[0014] In accordance with the present invention, an improved reformingcatalyst is obtained when the catalyst, during reduction with hydrogen,is simultaneously contacted with hydrogen and a nonmetallicchlorine-containing compound in a reactor of a series of multiplereactors, and thereafter a hydrogen purge is maintained for a sufficientamount of time to expose the reforming catalyst to about 100 to about50,000 cubic feet of hydrogen per cubic foot of catalyst prior tobringing the system to reforming conditions.

[0015] Thus, in accordance with one aspect of the present invention,there is provided a process for the activation of a platinum reformingcatalyst contained in a multiple reaction zone system, said processcomprises: (a) reducing the catalyst with hydrogen; (b) simultaneouslywith step (a) contacting the catalyst with a nonmetallicchlorine-containing compound by introducing the nonmetallicchlorine-containing compound into a reaction zone of the multiplereaction zone system under conditions to effect decomposition of thenonmetallic chlorine-containing compound; and (c) thereafter purging theresulting chlorine-treated catalyst with hydrogen for a period of timenecessary to remove excess chlorine from the catalyst prior to the useof said chlorine-treated catalyst in a reforming process.

[0016] In accordance with another aspect of the present invention, thereis provided an improved process for the regeneration of a platinumreforming catalyst contained in a multiple reaction zone system, saidprocess comprises: (a) purging the multiple reaction zone system withnitrogen; (b) subjecting the deactivated catalyst to an oxidativeburning off at a temperature and for a time sufficient to removesubstantially all carbonaceous deposits thereon; (c) subjecting thesubstantially-carbon-free catalyst to an oxygen treatment for a periodof time sufficient to effect the oxidation of metals contained in thesubstantially-carbon-free catalyst; (d) purging the resulting oxidizedcatalyst of molecular oxygen; (e) cooling the resulting purged catalyst;(f) reducing the dried catalyst by contacting with hydrogen which isintroduced into a reaction zone of the multiple reaction zone system;(g) simultaneously with step (f) contacting the catalyst with anonmetallic chlorine-containing compound by introducing thechlorine-containing compound into a reactor of the multiple reactionzone system; and (h) thereafter purging the resulting catalyst systemsof steps (f) and (g) with hydrogen for a period of time necessary toremove excess chlorine from the catalyst prior to start up of themultiple reaction zone reforming system.

DETAILED DESCRIPTION OF THE INVENTION

[0017] In carrying out the process of the present invention there isemployed a treatment of the catalyst beds of a reforming system whichemploys a series of reactors, generally three or four, which can containvarying catalyst compositions in each of the reactors. The individualreactors of the series can contain a platinum-alumina catalyst systemeither alone or in combination with an additional metallic compound suchas rhenium, iridium, ruthenium, tin, palladium, germanium, and the like.It is presently preferred, in carrying out the regeneration andactivation processes of this invention that a platinum-rhenium-aluminacatalyst system be utilized in each reactor of the series.

[0018] The present invention is based upon the discovery that incarrying out the generally practiced procedure for regeneration ofreforming catalyst contained in a series of reactors, wherein thedeactivated catalyst is subjected to oxidation to remove carbonaceousdeposits and thereafter activated through the addition of achlorine-containing compound and hydrogen to the reactor system, or thatfresh catalyst is to be activated with hydrogen and achlorine-containing compound, that by introducing a nonmetallicchlorine-containing compound simultaneously with hydrogen to at leastone of the reactors, preferably to only the first of the reactors of theseries and thereafter purging the resulting activated catalyst systemwith from about 100 to about 50,000 cubic feet of hydrogen per cubicfeet of catalyst there is achieved a suitably activated catalyst which,when placed in service in the reforming process, provides a system inwhich undesirable cracking of the feedstock decreases while octanenumber of the reforming process product and catalyst activity increases.

[0019] In accordance with this invention, a reforming catalystcontaining a platinum metal is activated by simultaneously contactingthe catalyst with hydrogen and a nonmetallic chlorine-containingcompound, and thereafter purging the thus-treated catalyst withhydrogen.

[0020] An essential aspect of this invention is that the chloridetreatment of the catalyst must be performed simultaneously with hydrogenreduction of the catalyst. Chloride treatment is carried out by adding achlorine-containing compound to a reforming reactor while simultaneouslyreducing the catalyst within the reactors with hydrogen. Thechlorine-containing compound employed in the chloride treatment ispreferably a nonmetallic chloride. Nonmetallic chlorine-containingcompounds are preferred; because, contacting the catalyst with metallicchlorine-containing compounds tends to result in the build-up on thecatalyst of undesirable metals, which lead to reduced activity, reducedselectivity, or both. More preferably the chlorine-containing compoundis a nonmetallic organic chloride. Organic chlorides are preferredbecause they tend to decompose better under activation conditions in thereformer. Preferred nonmetallic organic chlorides include, for example,tetrachloroethylene, hexachloroethane, carbon tetrachloride,1-chlorobutane, 1-chloro-2-methyl propane, 2-chloro-2-methyl propane,tertiary butyl chloride, propylene dichloride, perchloroethylene, andmixtures of two or more thereof. The presently most preferrednon-metallic chloride is perchloroethylene.

[0021] Generally, the quantity of chlorine-containing compound employedduring the chloride treatment must be sufficient to provide in thecatalyst system from about 0.05 to about 0.3 pounds of chlorine perpound of catalyst, preferably from about 0.1 to about 0.2 pounds ofchlorine per pound of catalyst. The temperature employed during chloridetreatment must be sufficient so as to effect decomposition of thechlorine-containing compound. The chloride treatment can be performed ata temperature of from about 500° F. to about 1,500° F., preferably fromabout 700° F. to about 1,200° F., and most preferably from about or 900°F. to or about 940° F., and a pressure in the range of about 0 to about600 psig, preferably about 50 to about 300 psig.

[0022] As mentioned above, the chloride treatment must occursimultaneously with, and under the same conditions as, reduction of thecatalyst with hydrogen. The quantity of hydrogen within the systemduring chloride treatment must be equal to the stoichiometric amountrequired to form hydrogen chloride with the chlorine obtained from thechlorine-containing compound. At the same time there must be asubstantial absence in the system of free oxygen or compounds thatdecompose at the treating conditions to produce free oxygen.

[0023] Following chloride treatment and reduction with hydrogen, it isessential that the system is purged with an amount of hydrogen necessaryto remove excess chlorine from the catalyst. The amount of hydrogenemployed during the purging process can be from about 100 to about50,000, preferably from about 500 to about 30,000, and most preferably1,000 to 10,000 cubic feet of hydrogen per cubic foot of catalyst. Thehydrogen purge can be conducted at a temperature from about 500° F. toabout 1,500° F., preferably about 800° F. to 1,100° F., and mostpreferably from 900° F. to 940° F., and a pressure in the range of about0 to about 600 psig, preferably about 50 to about 300 psig.

[0024] If the hydrogen purge is conducted in a manner which exposes thecatalyst to less than about 100 cubic feet of hydrogen per cubic foot ofcatalyst, the resulting catalyst will not meet the objects of thisinvention due to the existence of excessive chlorine on the catalyst. Ifthe hydrogen purge is conducted in a manner which exposes the catalystto more than about 50,000 cubic feet of hydrogen per cubic foot ofcatalyst, the resulting catalyst will not meet the objects of thisinvention because the catalyst will not contain sufficient chlorine.

[0025] While the above-described technique is applicable to theactivation of substantially carbon-free fresh catalyst, it isparticularly advantageous to incorporate such technique in a method forreactivating catalysts which have become deactivated through employmentin a reforming process (i.e., a combined regeneration-reactivationprocedure).

[0026] In accordance with this embodiment, the invention is directed toa method for regenerating and activating a reforming catalyst containingplatinum metals that has become deactivated through a series ofreforming-regeneration cycles. This method comprises first purging thedeactivated catalyst with an inert gas, such as nitrogen. Thensubjecting the deactivated catalyst to an oxidative bum off at atemperature and period of time sufficient to remove substantially allcarbonaceous deposits therefrom. Quite commonly this oxidative bum-offis accomplished in two phases, the first of which is principally acarbon burn-off phase, while the second phase can be termed anafterburn.

[0027] In accordance with this technique, the carbon burn-off of theinventive process can be effected by contacting the carbon-containingcatalyst with an oxygen-containing gas, preferably a molecularoxygen-containing gas, having a comparatively low oxygen content whichis less than about 1 percent by volume, more preferably, between 0.2 and0.8 percent by volume. The temperature employed in the carbon bum-offtechnique ranges from a minimum temperature necessary to effectoxygen-containing of the carbon in the presence of the oxygen-containinggas up to a maximum temperature of about 1,200° F., preferably fromabout 300° F. to about 850° F.

[0028] In the afterburn phase, generally a gas of a comparatively higheroxygen content is employed, e.g. up to about 2 percent by volume ofoxygen. In this afterburn technique the maximum temperature employed isabout 1,300° F., preferably the temperature should be from about 400° F.to about 950° F. The temperature in both the carbon burn-off andafterburn phases can readily be controlled by adjusting of the oxygencontent of the oxygen-containing gas.

[0029] The catalyst resulting from the oxidative burn off should besubstantially carbon free, with from 80 percent upwardly to 100 percentof the carbon originally on the catalyst being burned off. Thesubstantially carbon free catalyst will thus generally have less thanabout one weight percent carbon but, more particularly, suchsubstantially carbon free catalyst will contain carbon in the range offrom about 0.01 weight percent to about 0.75 weight percent, but,preferably, from 0.01 to 0.25 weight percent. Most preferably, thecarbon content will be less than 0.15 weight percent, thus, from 0.01 to0.15 weight percent. Generally, the oxidative burn off should beperformed from about 4 to about 36 hours, preferably from 8 to 18 hours.

[0030] After the oxidative burn off, the substantially-carbon-freecatalyst is subjected to an oxygen treatment with a gas containing atleast about 5 percent by volume of molecular oxygen at a temperature inthe range of from about 800° F. to about 1,150° F., preferably fromabout 900° F. to about 940° F. In this oxygen treatment step of theinvention, any suitable oxygen-containing gas can be employed including,for example, air or air diluted with an inert gas such a nitrogen.Preferably the oxygen-containing gas will be comprised of from about 5to about 15 percent by volume of molecular oxygen. The duration of theoxygen treatment can be quite brief or can be extended for a period of afew days. Generally, such treatment is for a period of from about 4hours to 36 hours.

[0031] While it is not necessary to employ superatmospheric pressures inthe oxygen treatment step, it is usually convenient to do so. Thus,total pressures up to about 300 psig can be employed although normallythe total pressure is maintained at a level below 100 psig. Preferablysuch treatment is carried out at a pressure in the range of about 25 toabout 60 psig.

[0032] After the oxygen treatment step, the catalyst is purged ofmolecular oxygen. The purging can be conducted by any of the techniqueswell known in the art such as, for example, by flowing an inert gas suchas nitrogen through the catalyst.

[0033] After being purged of molecular oxygen, or simultaneouslytherewith, the catalyst is cooled to a temperature in the range of about600° F. to about 1,000° F., preferably about 800° F. to about 840° F.

[0034] After the catalyst has been freed of molecular oxygen and cooled,it is then activated in substantially the same manner as describedpreviously. As described in detail above, activation is accomplished bysimultaneously contacting the catalyst with hydrogen and achlorine-containing compound, and thereafter purging the catalyst withhydrogen.

[0035] The following examples are intended to be illustrative of thepresent invention and to teach one of ordinary skill in the art to makeand use the invention. These examples are not intended to limit theinvention in any way.

EXAMPLE I

[0036] This example demonstrates activation of a reforming catalyst byreducing the catalyst with hydrogen while contacting the catalyst with achlorine-containing compound.

[0037] A stainless-steel reactor having an inner diameter of about 0.75inches and a height of about 28 inches was filled with a bottom layer ofabout 13.5 inches of inert alumina particles having a surface area of 1m²/g or less, a middle layer of about 6 inches (20 cubic centimeters) ofR-56 Pt/alumina reforming catalyst marketed by UOP, Des Plaine, Il.(containing about 0.25 weight percent platinum, about 0.40 weightpercent rhenium and about 1.0 weight percent Cl on gamma alumina), and atop layer of about 8 inches of inert alumina.

[0038] The catalyst system was activated at 940° F. by introducinghydrogen at 200 psig while adding perchloroethane at 32 microliters/hrfor 15 minutes to give 0.2 weight percent chloride on the catalyst.

[0039] Thereafter, a liquid naphtha feed having 23% paraffins, 30%isoparaffins, 8% aromatics and 39% naphthenes was introduced into thereactor at a liquid-volume hourly space velocity of 2.0 hr⁻¹. Thereaction pressure was about 200 psig. The reaction temperature was about860° F. The liquid naphtha had an initial boiling point of 177° F. andan end point of 258° F. and an average molecular weight of 99.8.

[0040] The liquid naphtha feed was added in an amount such that thehydrogen to hydrocarbon ratio was 4.0.

[0041] Perchloroethane was then added to this system in an amount of 1.3ppm to the hydrocarbon feed.

[0042] The initial feed had a C5+ content of 100%, a RON value of 62 anda relative octane number of 100%.

[0043] After 24 hours of operation of the system, which did not have ahydrogen purge treatment prior to the introduction of the feed, theresults were as follows: C5+ product RON Relative OCT-Bbl, %By-Product⁽¹⁾ 74.6 84.4 102 1.96

EXAMPLE II

[0044] This example demonstrates activation of a catalyst in the mannershown in Example I, except after the hydrogen reduction and chloridetreatment the catalyst was purged with hydrogen. The hydrogen purge, ata rate of 1.3 SCF per hour, was carried out for a period of 2.0 to 7hours at about 940° F. and 200 psig following the activation of thecatalyst system with perchloroethylene addition and prior to theintroduction of the naphtha feed to the system.

[0045] The results of the test were as follows: Purge Time C5+ RelativeOCT-Bbl, (hrs) product RON % By-Product⁽¹⁾ 2 84.4 86.2 117 1.47 2.5 86.984.5 118 1.63 7 59.9 86.1  83 2.36

[0046] The above data demonstrates that the use of a hydrogen purge at arate of 1.3 SCF of hydrogen per hour for a period up to about 2.5 hours(a time sufficient to provide 4,600 cubic feet of hydrogen per cubicfoot of catalyst) after activation of the catalyst system by theaddition of chlorine and prior to the introduction of a naphtha feedresults in a reforming system which has reduced cracking of productwhile achieving an increase in RON values. The data further demonstratesthat purge times which expose the catalyst to either too much or toolittle hydrogen produce less favorable result.

EXAMPLE III

[0047] This example demonstrates activation of a catalyst in the mannershown in Example I, except the reaction temperature is 840° F. ratherthan 860° F.

[0048] After 24 hours of operation of the system, which did not have ahydrogen purge treatment prior to the introduction of the feed, theresults were as follows: C5+ product RON Relative OCT-Bbl, %By-Product⁽¹⁾ 86.6 80.4 112 1.55

EXAMPLE IV

[0049] This example demonstrates activation of a catalyst in the mannershown in Example III, except after the hydrogen reduction and chloridetreatment the catalyst was purged with hydrogen. The hydrogen purge, ata rate of 1.3 SCF per hour, was carried out for a period of 0.5 to 22hours at about 940° F. and 200 psig following the activation of thecatalyst system with perchloroethylene addition and prior to theintroduction of the naphtha feed to the system.

[0050] The results of the test were as follows: Purge Time C5+ RelativeOCT-Bbl, (hrs) product RON % By-Product⁽¹⁾ 0.5 91.7 83.9 124 0.92 2261.6 68  68 2.00

[0051] The above data demonstrates that the use of a hydrogen purge at arate of 1.3 SCF of hydrogen per hour for a period of 0.5 hours (a timesufficient to provide 920 cubic feet of hydrogen per cubic foot ofcatalyst) after activation of the catalyst system by the addition ofchlorine and prior to the introduction of a naphtha feed results in areforming system which has reduced cracking while achieving an increasein RON values. The data further illustrates that purge times whichexpose the catalyst to either too much or too little hydrogen, produceless favorable results.

[0052] The specific examples herein disclosed are to be considered asbeing primarily illustrative. Various changes beyond those describedwill no doubt occur to those skilled in the art; and such changes are tobe understood as forming a part of this invention insofar as they fallwithin the spirit and scope of the appended claims.

That which is claimed is:
 1. A process for activating aplatinum-containing reforming catalyst contained in a multiple reactionzone system, said process comprises: (a) reducing saidplatinum-containing reforming catalyst with hydrogen; (b) simultaneouslywith step (a) contacting said platinum-containing reforming catalystwith a nonmetallic chlorine-containing compound by introducing saidnonmetallic chlorine-containing compound into a reaction zone of saidmultiple reaction zone system under conditions to effect decompositionof said nonmetallic chlorine-containing compound thereby providing achlorine-treated catalyst; and (c) thereafter purging saidchlorine-treated catalyst with about 100 to about 50,000 cubic feet ofhydrogen per cubic foot of said chlorine-treated catalyst prior to usingsaid chlorine-treated catalyst in a reforming process.
 2. A processaccording to claim 1 wherein said contacting is carried out at atemperature in the range of about 700° F. to about 1,200° F. and apressure in the range of about 0 to about 600 psig.
 3. A processaccording to claim 2 wherein said purging is carried out at atemperature in the range of about 800° F. to about 1,100° F. and apressure in the range of about 0 to about 600 psig.
 4. A processaccording to claim 1 wherein said nonmetallic chlorine-containingcompound is added to said platinum-containing reforming catalyst in anamount sufficient to add from 0.05 to about 0.3 pounds of chlorine perpound of said platinum-containing reforming catalyst.
 5. A processaccording to claim 4 wherein said nonmetallic chlorine-containingcompound is selected from the group consisting of tetrachloroethylene,hexachlorethane, carbon tetrachloride, 1-chlorobutane, 1-chloro-2-methylpropane, 2-chloro-2-methyl propane, tertiary butyl chloride, propylenedichloride, perchloroethylene, and mixtures of two or more thereof.
 6. Aprocess according to claim 5 wherein said nonmetallicchlorine-containing compound is perchloroethylene.
 7. A process forregenerating a deactivated reforming catalyst contained in a multiplereaction zone system and which has become deactivated through employmentin the reforming of a hydrocarbon, said process comprises: (a) purgingsaid multiple reaction zone system with nitrogen; (b) subjecting saiddeactivated reforming catalyst to an oxidative burning off at atemperature and for a period of time sufficient to remove substantiallyall carbonaceous deposits thereon thereby providing a substantiallycarbon free catalyst; (c) subjecting said substantially carbon freecatalyst to an oxygen treatment with a gas containing molecular oxygenat a temperature and for a time sufficient to effect the oxidation ofthe metals contained in said substantially carbon free catalyst therebyproviding an oxidized catalyst; (d) purging said oxidized catalyst ofmolecular oxygen thereby providing a purged catalyst; (e) cooling saidpurged catalyst thereby providing a cooled catalyst; (f) reducing saidcooled catalyst with hydrogen, said hydrogen being introduced into areaction zone of said multiple reaction zone system; (g) simultaneouslywith step (f) contacting said cooled catalyst with a nonmetallicchlorine-containing compound in a quantity sufficient to provide fromabout 0.05 to about 0.3 weight percent chlorine on said cooled catalystby introducing said nonmetallic chlorine-containing compound into saidreaction zone of said multiple reaction zone system under conditions toeffect decomposition of said nonmetallic chlorine-containing compoundthereby providing a chlorine-treated catalyst; (h) thereafter purgingsaid chlorine-treated catalyst with about 100 to about 50,000 cubic feetof hydrogen per cubic foot of said chlorine-treated catalyst at atemperature in the range of about 700° F. to about 1,200° F. and apressure in the range of about 0 to about 600 psig prior to introducinghydrocarbon into said multiple reaction zone system.
 8. A processaccording to claim 7 wherein said oxidative burning off step (b) iscarried out at a temperature in the range of from about 300° F. to about1,300° F. and for a period of time in the range of about 4 to about 36hours.
 9. A process according to claim 8 wherein said oxygen treatmentstep (c) said gas contains from about 5 to about 15 percent by volume ofmolecular oxygen.
 10. A process according to claim 9 wherein said oxygentreatment step (c) is carried out at a temperature in the range of about800° F. to about 1,150° F.
 11. A process according to claim 7 whereinsaid purged catalyst is cooled to a temperature in the range of about600° F. to about 1,000° F.
 12. A process according to claim 7 whereinstep (f) and step (g) are carried out at a temperature in the range ofabout 900° F. to about 940° F. and at a pressure in the range of fromabout 50 to about 300 psig.
 13. A process according to claim 7 whereinsaid deactivated reforming catalyst is a platinum-on-alumina reformingcatalyst.
 14. A process according to claim 13 wherein saidplatinum-on-alumina reforming catalyst also contains at least one metalselected from the group consisting of rhenium, iridium, ruthenium, tin,palladium, germanium, and combinations of two or more thereof.
 15. Aprocess according to claim 7 wherein said nonmetallicchlorine-containing compound is selected from the group consisting oftetrachloroethylene, hexachlorethane, carbon tetrachloride1-chlorobutane, 1-chloro-2-methyl propane, 2-chloro-2-methyl propane,tertiary butyl chloride, propylene dichloride, perchloroethylene, andmixtures of two or more thereof.
 16. A process according to claim 15wherein said nonmetallic chlorine-containing compound isperchloroethylene.
 17. In a process for reforming naphthene andparaffin-containing petroleum hydrocarbons of gasoline or naphthaboiling range in the presence of molecular hydrogen wherein there isemployed in series a plurality of catalytic reaction zones to providereformates, the improvement which comprises utilizing in said catalyticreaction zones a catalyst activated by the process of claim 1 .
 18. In aprocess for reforming naphthene and paraffin-containing petroleumhydrocarbons of gasoline or naphtha boiling range in the presence ofmolecular hydrogen wherein there is employed in series a plurality ofcatalytic reaction zones to provide reformates, the improvement whichcomprises using said catalytic reaction zone a catalyst regenerated andactivated by the process of claim 7 .
 19. The activated catalyst systemof claim 1 .
 20. The activated catalyst system of claim 7 .